ijms-logo

Journal Browser

Journal Browser

Chemical Tuning of Molecular Magnetic and Optical Materials

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Materials Science".

Deadline for manuscript submissions: closed (15 November 2022) | Viewed by 4184

Special Issue Editors


E-Mail Website
Guest Editor
Department of Inorganic Chemistry, Jagiellonian University, PL-30387 Krakow, Poland
Interests: molecule-based magnets; molecular ionic conductors; stimuli-responsive molecular materials, switchable functional materials; charge-transfer phenomena

E-Mail Website
Guest Editor
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Poland
Interests: functional molecular materials; luminescent materials; molecule-based magnets; stimuli-responsive materials; optical thermometers; chiral materials; multifunctionality; cyanido metal complexes; lanthanides

Special Issue Information

Dear Colleagues,

Molecular materials have a unique ability to translate the properties of their molecular building blocks into macroscopic features. Numerous studies have shown that a bottom-up approach serves well as a rational strategy in the design of functional materials, whose functionalities cover a wide spectrum of properties. Indeed, molecular materials unlock a variety of properties that are not achievable in conventional alloy- or oxide-based materials. In particular, molecular magnetism and molecular optics have been discovered and broadly developed, which may offer practical solutions for such important problems as efficient storage and fast processing of data. By the use of quantum effects, rooted in the molecular level of such materials, peculiar properties emerged, such as single-molecule or single-chain magnet behaviour. Moreover, molecular materials often can respond to the application of external stimuli, both physical and chemical, by the change of certain properties, e.g., magnetic, absorption, or luminescent ones. Responsivity to a chemical stimulus is particularly interesting in such materials as it may be utilized in the construction of small molecule sensors or chemical-to-physical information convertors. The last few years have shown that we can effectively design and synthesize chemically switchable materials with a significant and easy-to-measure physical response to such a stimulus, which brings us closer to real-life applications.

This Special Issue Chemical tunning of molecular magnetic and optical materials welcomes original research papers and reviews discussing molecular materials whose magnetic and optical features are controlled by chemical stimuli. In this issue, we would like to highlight recent and significant achievements in the field and draw a perspective on the further development of chemically tuned molecular magnetic and optical materials, such as molecular nanomagnets, spin transition materials, luminescent molecular magnets, luminescent thermometers, vapochromic systems. We aim to gather current knowledge concerning the design, synthesis, development, and characterisation of such chemo-responsive molecular systems.

Dr. Mateusz Reczyński
Dr. Szymon Chorazy
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. International Journal of Molecular Sciences is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. There is an Article Processing Charge (APC) for publication in this open access journal. For details about the APC please see here. Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • molecular materials
  • stimuli-responsive materials
  • sensors
  • molecular magnets
  • spin transition materials
  • luminophores
  • vapochromic systems
  • luminescent magnets
  • optical thermometry

Published Papers (3 papers)

Order results
Result details
Select all
Export citation of selected articles as:

Research

15 pages, 2486 KiB  
Article
Sensing Magnetic Field and Intermolecular Interactions in Diamagnetic Solution Using Residual Dipolar Couplings of Zephycandidine
by Radoslaw M. Kowalczyk, Patrick J. Murphy and Jamie Tibble-Howlings
Int. J. Mol. Sci. 2022, 23(23), 15118; https://doi.org/10.3390/ijms232315118 - 1 Dec 2022
Viewed by 806
Abstract
An unusual residual dipolar coupling of methylene protons was recorded in NMR spectra because aromatic zephycandidine has preferential orientation at the external magnetic field. The observed splitting contains contribution from the dipole–dipole D-coupling and the anisotropic component of J-coupling. Absolute values [...] Read more.
An unusual residual dipolar coupling of methylene protons was recorded in NMR spectra because aromatic zephycandidine has preferential orientation at the external magnetic field. The observed splitting contains contribution from the dipole–dipole D-coupling and the anisotropic component of J-coupling. Absolute values of the anisotropy of magnetic susceptibility |Δχax| are larger for protic solvents because of the hydrogen-bonding compared to aprotic solvents for which polar and dispersion forces are more important. The energy barrier for the reorientation due to hydrogen-bonding is 1.22 kJ/mol in methanol-d4, 0.85 kJ/mol in ethanol-d6 and 0.87 kJ/mol in acetic acid-d6. In dimethyl sulfoxide-d6, 1.08 kJ/mol corresponds to the interaction of solvent lone pair electrons with π-electrons of zephycandidine. This energy barrier decreases for acetone-d6 which has smaller electric dipole moment. In acetonitrile-d3, there is no energy barrier which suggests solvent ordering around the solute due to the solvent-solvent interactions. The largest absolute values of the magnetic anisotropy are observed for aromatic benezene-d6 and tolune-d8 which have their own preferential orientation and enhance the order in the solution. The magnetic anisotropy of “isolated” zephycandidine, not hindered by intermolecular interaction could be estimated from the correlation between Δχax and cohesion energy density. Full article
(This article belongs to the Special Issue Chemical Tuning of Molecular Magnetic and Optical Materials)
Show Figures

Figure 1

25 pages, 6864 KiB  
Article
Electro-Elastic Modeling of Thermal Spin Transition in Diluted Spin-Crossover Single Crystals
by Karim Affes, Yogendra Singh and Kamel Boukheddaden
Int. J. Mol. Sci. 2022, 23(22), 13854; https://doi.org/10.3390/ijms232213854 - 10 Nov 2022
Cited by 2 | Viewed by 1229
Abstract
Spin-crossover solids have been studied for many years for their promising applications as optical switches and reversible high-density memories for information storage. This study reports the effect of random metal dilution on the thermal and structural properties of a spin-crossover single crystal. The [...] Read more.
Spin-crossover solids have been studied for many years for their promising applications as optical switches and reversible high-density memories for information storage. This study reports the effect of random metal dilution on the thermal and structural properties of a spin-crossover single crystal. The analysis is performed on a 2D rectangular lattice using an electro-elastic model. The lattice is made of sites that can switch thermally between the low-spin and high-spin states, accompanied by local volume changes. The model is solved by Monte Carlo simulations, running on the spin states and atomic positions of this compressible 2D lattice. A detailed analysis of metal dilution on the magneto-structural properties allows us to address the following issues: (i) at low dilution rates, the transition is of the first order; (ii) increasing the concentration of dopant results in a decrease in cooperativity and leads to gradual transformations above a threshold concentration, while incomplete spin transitions are obtained for big dopant sizes. The effects of the metal dilution on the spatiotemporal aspects of the spin transition along the thermal transition and on the low-temperature relaxation of the photo-induced metastable high-spin states are also studied. Significant changes in the organization of the spin states are observed for the thermal transition, where the single-domain nucleation caused by the long-range elastic interactions is replaced by a multi-droplet nucleation. As to the issue of the relaxation curves: their shape transforms from a sigmoidal shape, characteristic of strong cooperative systems, into stretched exponentials for high dilution rates, which is the signature of a disordered system. Full article
(This article belongs to the Special Issue Chemical Tuning of Molecular Magnetic and Optical Materials)
Show Figures

Figure 1

15 pages, 1887 KiB  
Article
Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence
by Kunal Kumar, Olaf Stefanczyk, Koji Nakabayashi, Yuuki Mineo and Shin-ichi Ohkoshi
Int. J. Mol. Sci. 2022, 23(11), 6051; https://doi.org/10.3390/ijms23116051 - 27 May 2022
Cited by 5 | Viewed by 1608
Abstract
Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [NdIII [...] Read more.
Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [NdIII (phen)3 (NCX)3] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN by SeCN. Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300–150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption. Full article
(This article belongs to the Special Issue Chemical Tuning of Molecular Magnetic and Optical Materials)
Show Figures

Figure 1

Back to TopTop